The formation of high aspect ratio organosiloxane fibers of nanodimensionality via the surface-induced vapor-phase polymerization of vinyltrichlorosilane is reported. We also demonstrate the versatility of our method by producing fibers of various densities, polydispersities, and lengths. Nanofibers were characterized using SEM, EDX, XPS, TOF-SIMS, and variable-angle FTIR. Advancing aqueous contact angle measurements were used to evaluate the nanofiber surface wettability.